CN114249991A - Modified nano titanium dioxide material and preparation method and application thereof - Google Patents
Modified nano titanium dioxide material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a modified nano titanium dioxide material, which comprises the following components in percentage by weight: the surface is grafted with micromolecular nano titanium dioxide; wherein the small molecule is a nucleotide or an amino acid. By grafting amino acid or nucleotide micromolecules on the surface of the nano titanium dioxide, steric hindrance is generated among nano titanium dioxide particles, the secondary agglomeration phenomenon among the nano titanium dioxide particles is effectively overcome, and the modified nano titanium dioxide material with better dispersion performance is obtained. In addition, the antibacterial performance of the modified nano titanium dioxide material is obviously enhanced. Furthermore, the raw materials required by the modified nano titanium dioxide material are safe, nontoxic and cheap, and can be industrially produced in an enlarged way.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a modified nano titanium dioxide material and a preparation method and application thereof.
Background
The nano material has surface effect, small size effect, quantum effect and macroscopic quantum tunnel effect, and has obviously different properties in the aspects of optics, heat, electricity, magnetism, mechanics and chemistry compared with bulk materials, so the nano material is widely applied in a plurality of fields.
As a functional fine inorganic material with high added value, the nano titanium dioxide has the characteristics of small particle size, large specific surface area, strong photocatalytic activity, good absorption performance, strong ultraviolet ray absorption capacity, large surface activity, good thermal conductivity, good weather resistance, corrosion resistance, strong ultraviolet ray resistance and the like, has better stability, is nontoxic and harmless to a human body, has no secondary pollution, is low in price and has wide application prospect in multiple aspects.
The performance of the nano product depends on the dispersion degree of the nano particles to a great extent, but the nano titanium dioxide has small particle size, large specific surface area and high specific surface energy, so that the nano titanium dioxide particles are easy to agglomerate to form secondary particles due to van der Waals force and coulomb force existing among the particles in the preparation process or the post-treatment process, and the original physical properties and functions of the particles are lost in the final application. Meanwhile, to a certain extent, the nano titanium dioxide particles have low toxicity to organisms, and the toxicity of large particles formed after the nano titanium dioxide particles are agglomerated to the organisms is obviously enhanced. Therefore, the strong polarity of the nano titanium dioxide particles and the micronization of the particles enable the nano titanium dioxide particles to be difficult to disperse in a non-polar medium and easy to agglomerate in a polar medium, and the antibacterial performance and other performances of the nano titanium dioxide particles are directly influenced, so that the application of the nano titanium dioxide particles is limited.
Disclosure of Invention
Based on the modified nano titanium dioxide material, the modified nano titanium dioxide material has the advantages of good dispersibility, difficult agglomeration and strong antibacterial property.
The invention is realized by the following technical scheme.
A modified nano titania material, comprising: the surface is grafted with micromolecular nano titanium dioxide;
wherein the small molecule is a nucleotide or an amino acid.
In one embodiment, the nucleotides are selected from adenosine triphosphate or adenine.
In one embodiment, the amino acid is selected from L-threonine or L-cysteine.
In one embodiment, the mass ratio of the small molecules to the nano titanium dioxide is (0.1-1): 1.
The invention also provides application of the modified nano titanium dioxide material in coatings, plastics, ceramics or non-woven fabrics.
The invention also provides a preparation method of the modified nano titanium dioxide material, which comprises the following steps:
mixing the nano titanium dioxide, the micromolecules and a dispersion medium, and grinding.
In one embodiment, the milling is performed by ball milling.
In one embodiment, the milling media used for ball milling is zirconia beads.
In one embodiment, the zirconia beads have a particle size of 0.1mm to 0.5 mm.
In one embodiment, the ball milling conditions include: the rotating speed is 200 r/min-800 r/min; the time is 1-8 h.
In one embodiment, the mass ratio of the nano titanium dioxide to the dispersion medium is 1: 100-1: 10000.
In one embodiment, the dispersion medium is water.
Compared with the prior art, the modified nano titanium dioxide material has the following beneficial effects:
according to the invention, amino acid or nucleotide micromolecules are grafted to the surface of the nano titanium dioxide, so that steric hindrance is generated among the nano titanium dioxide particles, and the secondary agglomeration phenomenon among the nano titanium dioxide particles is effectively overcome, thus the modified nano titanium dioxide material with better dispersion performance is obtained, the particle size of the modified nano titanium dioxide is about 70nm, the original excellent performance of the nano titanium dioxide is ensured, compared with a single nano titanium dioxide material, the antibacterial performance of the modified nano titanium dioxide is obviously enhanced, and the MIC value of the modified nano titanium dioxide to escherichia coli and staphylococcus aureus is dozens or even one hundredth of that of the nano titanium dioxide before modification.
Furthermore, the raw materials required by the modified nano titanium dioxide material are safe, nontoxic and cheap, and can be industrially produced in an enlarged way.
Drawings
FIG. 1 is a diagram of a product provided by the present invention; wherein (a) represents nano titanium dioxide, and (b) represents L-threonine modified nano titanium dioxide;
FIG. 2 is a Fourier infrared spectrum provided by the present invention;
FIG. 3 is a transmission electron microscope image provided by the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
The words "preferably," "more preferably," and the like, in the present disclosure mean embodiments of the disclosure that may, in some instances, provide certain benefits. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a modified nano titanium dioxide material, which comprises the following components in part by weight: the surface is grafted with micromolecular nano titanium dioxide;
wherein, the small molecule is nucleotide or amino acid.
The nucleotide or amino acid small molecule as natural component of human body can provide raw material for in vivo nucleic acid or protein synthesis, and has effects of nourishing and providing energy. Therefore, these small molecules are beneficial and harmless to the human body.
In a specific example, the nano-titania is anatase-type nano-titania. More specifically, the nano titanium dioxide is anatase type nano titanium dioxide powder.
In a specific example, the nano titanium dioxide has a particle size of 800nm to 1000 nm.
It is understood that in the present invention, the particle size of the nano titanium dioxide includes, but is not limited to, 800nm, 810nm, 820nm, 830nm, 840nm, 850nm, 860nm, 870nm, 880nm, 890nm, 900nm, 910nm, 920nm, 930nm, 940nm, 950nm, 960nm, 970nm, 980nm, 990nm, 1000 nm.
In a preferred example, the nano-titania is 99.9% pure.
In a preferred example, the small molecules are selected from food grade.
In a specific example, the nucleotides are selected from adenosine triphosphate or adenine.
In a specific example, the amino acid is selected from L-threonine or L-cysteine. In a preferred embodiment, the amino acid is selected from L-threonine.
In a specific example, the particle size of the nano titanium dioxide grafted with small molecules on the surface is 70 nm-90 nm. Preferably, the particle size of the nano titanium dioxide grafted with small molecules on the surface is 70 nm.
In a specific example, the mass ratio of the small molecules to the nano titanium dioxide is (0.1-1): 1.
It is understood that the mass ratio of small molecule to nano titania includes, but is not limited to, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1: 1.
The invention also provides an application of the modified nano titanium dioxide material in a coating, plastics, ceramics or non-woven fabrics.
The invention also provides a preparation method of the modified nano titanium dioxide material, which comprises the following steps:
mixing the nano titanium dioxide, the micromolecules and the dispersion medium, and grinding.
In one specific example, the milling is by ball milling.
In one particular example, the milling media used for ball milling are zirconia beads.
In a specific example, the zirconia beads have a particle size of 0.1mm to 0.5 mm.
It is understood that the particle size of the zirconia beads includes, but is not limited to, 0.10mm, 0.20mm, 0.30mm, 0.40mm, 0.50 mm. In a preferred example, the zirconia beads have a particle size of 0.1 mm.
In one specific example, the ball milling conditions include: the rotation speed of the ball milling is 200 r/min-800 r/min.
It is understood that in the present invention, the rotational speed of the ball mill includes, but is not limited to, 200r/min, 220r/min, 240r/min, 260r/min, 280r/min, 300r/min, 320r/min, 340r/min, 360r/min, 380r/min, 400r/min, 420r/min, 440r/min, 460r/min, 480r/min, 500r/min, 520r/min, 540r/min, 560r/min, 580r/min, 600r/min, 620r/min, 640r/min, 660r/min, 680r/min, 700r/min, 720r/min, 740r/min, 760r/min, 780r/min, 800 r/min.
In one specific example, the ball milling conditions include: the ball milling time is 1-8 h.
It is understood that in the present invention, the time period of ball milling includes, but is not limited to, 1.0h, 1.5h, 2h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5h, 6.0h, 6.5h, 7.0h, 7.5h, 8.0 h.
In a specific example, the mass ratio of the small molecules to the nano titanium dioxide is (0.1-1): 1.
It is understood that the mass ratio of the small molecule to the nano titanium dioxide in the present invention includes, but is not limited to, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1: 1. In a preferred example, the mass ratio of the small molecule to the nano titania is 0.2: 1.
In a specific example, the mass ratio of the nano titanium dioxide to the dispersion medium is 1:100 to 1: 10000.
It is understood that the mass ratio of the dispersion medium to the nano titanium dioxide in the present invention includes, but is not limited to, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 2000:1, 3000:1, 4000:1, 5000:1, 6000:1, 7000:1, 8000:1, 9000:1, 10000: 1.
In one particular example, the dispersion medium is water. More specifically, the pH of the water is 7.0. The pH value of the reaction system is set to be 7.0, and the environment is not greatly polluted.
In a preferred example, the water is purified water.
In a preferred example, the conditions for the mechanical-chemical modification by ball milling are normal temperature and pressure, and the temperature in the ball milling tank is increased due to the collision of the milling media during the ball milling.
In a preferred example, the ball mill is a high-energy planetary ball mill. After the nanometer titanium dioxide reaches the nanometer level through the high-energy ball milling, reaction sites are formed on the surface and are grafted with micromolecule amino acid or micromolecule nucleotide, and steric hindrance is formed among the nanometer titanium dioxide particles, so that the phenomenon that the nanometer titanium dioxide tends to agglomerate due to the instability of the reduced particle size is effectively overcome.
In a more specific example, the preparation method of the modified nano titanium dioxide material comprises the following steps:
adding zirconia beads with the particle size of 0.1-0.5 mm into a ball milling tank, weighing micromolecules, nano titanium dioxide and water with the mass ratio of (0.1-1): 1, (100-10000), placing the mixture into the ball milling tank for ball milling, setting the ball milling speed to be 200-800 r/min, setting the ball milling time to be 1-8 h, closing the ball milling tank after the experiment is finished, and taking out the dispersed modified nano titanium dioxide antibacterial colloidal solution in the ball milling tank at an interval of 20-40 min after the ball milling tank is cooled.
The modified nano-titania material and the preparation method thereof of the present invention will be described in further detail with reference to specific examples. The starting materials used in the following examples are all commercially available products unless otherwise specified. The purity of the adopted nano titanium dioxide is 99.9 percent, the adopted nano titanium dioxide is commercially available anatase powder, the selected micromolecules are food grade, and the adopted water is purified water self-made in a laboratory.
Example 1
The embodiment provides a preparation method of a modified nano titanium dioxide material, which comprises the following specific steps:
step one, weighing 100g of zirconia beads with the particle size of 0.1mm, pouring the zirconia beads into a 100ml agate ball milling tank, weighing 0.5g of anatase type nano titanium dioxide powder and 0.25g of micromolecule adenosine triphosphate, placing the powder into the 100ml agate ball milling tank, adding 50g of purified water into the agate ball milling tank, placing the powder into a ball mill, setting the rotating speed of the ball mill to be 800r/min, and setting the ball milling time to be 1 h.
And step two, closing the ball mill after the ball milling is finished, taking down the ball milling tank after the time interval is 30min, and taking out the adenosine triphosphate grafted nano titanium dioxide colloidal solution.
And step three, detecting the antibacterial performance of the adenosine triphosphate grafted nano titanium dioxide colloidal solution. Taking the nano titanium dioxide aqueous colloidal solution grafted by adenosine triphosphate as an antibacterial detection object, and carrying out a minimum inhibitory concentration determination test according to 'disinfection technical specification' 2002 edition 2.1.8.4. Testing strains: escherichia coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 2
The embodiment provides a preparation method of a modified nano titanium dioxide material, which comprises the following specific steps:
step one, weighing 100g of zirconia beads with the particle size of 0.1mm, pouring the zirconia beads into a 100ml agate ball milling tank, weighing 0.5g of anatase type nano titanium dioxide powder and 0.1g of micromolecule L-threonine, placing the powder into the 100ml agate ball milling tank, adding 50g of purified water into the agate ball milling tank, placing the powder into a ball mill, setting the rotating speed of the ball mill to be 600r/min, and setting the ball milling time to be 6 h.
And step two, closing the ball mill after the ball milling is finished, taking down the ball milling tank after the time interval is 30min, and taking out the L-threonine grafted nano titanium dioxide colloidal solution.
And step three, centrifuging the L-threonine grafted nano titanium dioxide colloidal solution, drying, and detecting by Fourier transform infrared spectroscopy (FTIR), wherein the obtained infrared spectrogram is shown in figure 2.
And step four, carrying out Transmission Electron Microscope (TEM) detection on the L-threonine grafted nano titanium dioxide colloidal solution, wherein an obtained TEM image is shown in FIG. 3.
And step five, detecting the antibacterial property of the L-threonine grafted nano titanium dioxide colloidal solution. The nano titanium dioxide aqueous colloidal solution grafted by L-threonine is used as an antibacterial detection object, and a minimum inhibitory concentration determination test is carried out according to the disinfection technical specification 2002 edition 2.1.8.4. Testing strains: escherichia coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 3
The embodiment provides a preparation method of a modified nano titanium dioxide material, which comprises the following specific steps:
step one, weighing 100g of zirconia beads with the particle size of 0.1mm, pouring the zirconia beads into a 100ml agate ball milling tank, weighing 0.05g of anatase type nano titanium dioxide powder and 0.05g of micromolecule L-cysteine, placing the powder into the 100ml agate ball milling tank, adding 50g of purified water into the agate ball milling tank, placing the powder into a ball mill, setting the rotating speed of the ball mill to be 200r/min, and setting the ball milling time to be 8 h.
And step two, closing the ball mill after the ball milling is finished, taking down the ball milling tank after the time interval is 30min, and taking out the L-cysteine grafted nano titanium dioxide colloidal solution.
And step three, detecting the antibacterial property of the L-cysteine grafted nano titanium dioxide colloidal solution. The nano titanium dioxide aqueous colloidal solution grafted by L-cysteine is used as an antibacterial detection object, and a minimum inhibitory concentration determination test is carried out according to the disinfection technical specification 2002 edition 2.1.8.4. Testing strains: escherichia coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 4
The embodiment provides a preparation method of a modified nano titanium dioxide material, which comprises the following specific steps:
step one, weighing 100g of zirconia beads with the particle size of 0.1mm, pouring the zirconia beads into a 100ml agate ball milling tank, weighing 0.5g of anatase type nano titanium dioxide powder and 0.1g of micromolecular adenine, placing the powder into the 100ml agate ball milling tank, adding 50g of purified water into the agate ball milling tank, placing the powder into a ball mill, setting the rotating speed of the ball mill to 600r/min, and setting the ball milling time to be 6 h.
And step two, closing the ball mill after the ball milling is finished, taking down the ball milling tank after the time interval of 30min, and taking out the nano titanium dioxide colloidal solution grafted by adenine.
And step three, detecting the antibacterial property of the nano titanium dioxide colloidal solution grafted with adenine. The nano titanium dioxide aqueous colloidal solution grafted by adenine is taken as an antibacterial detection object, and a minimum inhibitory concentration determination test is carried out according to the disinfection technical specification 2002 edition 2.1.8.4. Testing strains: escherichia coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 5
The embodiment provides a preparation method of a modified nano titanium dioxide material, which comprises the following specific steps:
step one, weighing 100g of zirconia beads with the particle size of 0.1mm, pouring the zirconia beads into a 100ml agate ball milling tank, weighing 0.5g of anatase type nano titanium dioxide powder and 0.5g of micromolecule L-threonine, placing the powder into the 100ml agate ball milling tank, adding 50g of purified water into the agate ball milling tank, placing the powder into a ball mill, setting the rotating speed of the ball mill to be 600r/min, and setting the ball milling time to be 6 h.
And step two, closing the ball mill after the ball milling is finished, taking down the ball milling tank after the time interval is 30min, and taking out the L-threonine grafted nano titanium dioxide colloidal solution.
And step three, detecting the antibacterial property of the L-threonine grafted nano titanium dioxide colloidal solution. The nano titanium dioxide aqueous colloidal solution grafted by L-threonine is used as an antibacterial detection object, and a minimum inhibitory concentration determination test is carried out according to the disinfection technical specification 2002 edition 2.1.8.4. Testing strains: escherichia coli ATCC25922, staphylococcus aureus ATCC 29213.
Example 6
The embodiment provides a preparation method of a modified nano titanium dioxide material, which comprises the following specific steps:
step one, weighing 100g of zirconia beads with the particle size of 0.5mm, pouring the zirconia beads into a 100ml agate ball milling tank, weighing 0.5g of anatase type nano titanium dioxide powder and 0.1g of micromolecule L-threonine, placing the powder into the 100ml agate ball milling tank, adding 50g of purified water into the agate ball milling tank, placing the powder into a ball mill, setting the rotating speed of the ball mill to be 600r/min, and setting the ball milling time to be 6 h.
And step two, closing the ball mill after the ball milling is finished, taking down the ball milling tank after the time interval is 30min, and taking out the L-threonine grafted nano titanium dioxide colloidal solution.
And step three, detecting the antibacterial property of the L-threonine grafted nano titanium dioxide colloidal solution. The nano titanium dioxide aqueous colloidal solution grafted by L-threonine is used as an antibacterial detection object, and a minimum inhibitory concentration determination test is carried out according to the disinfection technical specification 2002 edition 2.1.8.4. Testing strains: escherichia coli ATCC25922, staphylococcus aureus ATCC 29213.
Comparative example 1
The comparative example provides a preparation method of a modified nano titanium dioxide material, which comprises the following specific steps:
step one, weighing 0.5g of nano titanium dioxide powder, adding the nano titanium dioxide powder into 50g of pure water solution self-made by a laboratory, and setting ultrasonic time for 30 min.
And step two, centrifuging the ultrasonic nano titanium dioxide aqueous solution, drying to obtain powder, and performing Fourier infrared spectroscopy (FTIR) detection on the powder to obtain an infrared spectrogram as shown in figure 2.
And step three, carrying out transmission scanning electron microscope (TEM) detection on the nano titanium dioxide solution, wherein an obtained TEM image is shown in FIG. 3.
And step four, carrying out an antibacterial test on the nano titanium dioxide solution subjected to ultrasonic treatment. The nano titanium dioxide solution with good ultrasonic is taken as an antibacterial detection object, and a minimum inhibitory concentration determination test is carried out according to the disinfection technical specification 2002 edition 2.1.8.4. Testing strains: escherichia coli ATCC25922, staphylococcus aureus ATCC 29213.
Comparative example 2
The comparative example provides a preparation method of a modified nano titanium dioxide material, which is basically the same as the example 1, and mainly differs from the method that a mechanical stirring method is adopted to replace the step of ball milling. The method comprises the following specific steps:
weighing 0.5g of anatase type nano titanium dioxide powder, 0.25g of micromolecule adenosine triphosphate and 50g of purified water, placing the powder in a 50ml sample bottle, mechanically stirring at a high speed for 1h, keeping the stirring speed at 1000r/min, and standing for 30 min.
The solution product prepared by the comparative example does not successfully graft adenosine triphosphate on the surface of the nano titanium dioxide.
Fig. 1(a) shows a product in which nano titanium dioxide is ultrasonically dispersed in an aqueous solution emulsion, (b) shows a colloidal solution in which dispersed small molecule threonine is grafted on the surface of the nano titanium dioxide, and the comparison between (a) and (b) shows that the nano titanium dioxide aqueous solution after ultrasonic dispersion has poor dispersion effect and is easy to settle at the bottom under the same mass concentration, and the nano titanium dioxide aqueous solution after threonine grafting is subjected to ball milling modification, so that the nano titanium dioxide aqueous solution is clear and transparent and is not easy to aggregate, and the secondary aggregation of the nano titanium dioxide can be effectively overcome after the small molecule threonine is grafted on the surface of the nano titanium dioxide.
FIG. 2 shows the infrared spectrum of the emulsion of nano titanium dioxide dispersed in water solution by ultrasound and the infrared spectrum of the colloidal solution of dispersed small molecule L-threonine grafted on the surface of nano titanium dioxide, the surface of common nano titanium dioxide is inert and basically has no group, and the nano titanium dioxide grafted by small molecule L-threonine has some L-threonine groups after ball milling modification, and it can be found from the figure that 3407cm-1Is NH21628cm of telescopic vibration peak-1Is NH2Bending vibration peak of (2), 2347cm-1Is a stretching vibration peak of a C-H bond, and the characteristic peaks of the groups prove that after ball milling modification, the micromolecule L-threonine is successfully grafted to the surface of the nano titanium dioxide.
Fig. 3 is a transmission electron microscope image of an emulsion of nano titanium dioxide ultrasonically dispersed in an aqueous solution and a solution of dispersed small molecule threonine grafted nano titanium dioxide colloid, the nano titanium dioxide after ultrasonic treatment is seriously agglomerated, the particle size is about 600nm, and the nano titanium dioxide colloid solution after small molecule L-threonine grafting can be well dispersed and the particle size is about 75nm after ball milling modification, which shows that the small molecule L-threonine grafted nano titanium dioxide can well inhibit the secondary agglomeration to obtain the nano titanium dioxide colloid solution with stable dispersion.
The test data of the antibacterial properties of the solutions obtained in examples 1 to 6 and comparative example 1 are shown in tables 1 and 2, wherein the test bacterial species in table 1 is staphylococcus aureus, and the test bacterial species in table 2 is escherichia coli. The MIC value is a gradient decreasing test, and the final result is a gradient range according to the clarification degree of two test tubes.
As can be seen from tables 1 and 2, the MIC value of the nano titanium dioxide after ultrasonic dispersion is more than 5000ppm, the nano titanium dioxide basically has no antibacterial performance, and the nano titanium dioxide colloidal solution grafted by the micromolecules has better antibacterial performance after ball milling dispersion, especially when the mass ratio of the nano titanium dioxide powder to the micromolecules L-threonine is 5:1, the antibacterial performance is the best, the MIC values of the nano titanium dioxide colloidal solution grafted by the micromolecules L-threonine are both 16-32ppm and are close to 200 times of the nano titanium dioxide emulsion subjected to ultrasonic treatment, and the nano titanium dioxide colloidal solution grafted by the micromolecules L-threonine has very excellent antibacterial performance.
TABLE 1 antimicrobial Performance test
TABLE 2 antimicrobial Performance testing
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (12)
1. A modified nano titanium dioxide material, characterized in that the modified nano titanium dioxide material comprises: the surface is grafted with micromolecular nano titanium dioxide;
wherein the small molecule is a nucleotide or an amino acid.
2. The modified nano titanium dioxide material according to claim 1, wherein the nucleotide is adenosine triphosphate or adenine.
3. The modified nano titanium dioxide material according to claim 1, wherein the amino acid is L-threonine or L-cysteine.
4. The modified nano titanium dioxide material as claimed in claim 1, wherein the mass ratio of the small molecule to the nano titanium dioxide is (0.1-1): 1.
5. The use of the modified nano titanium dioxide material of any one of claims 1 to 4 in coatings, plastics, ceramics or non-woven fabrics.
6. The preparation method of the modified nanometer titanium dioxide material according to any one of claims 1 to 4, characterized by comprising the following steps:
mixing the nano titanium dioxide, the micromolecules and a dispersion medium, and grinding.
7. The preparation method of the modified nanometer titanium dioxide material as claimed in claim 6, characterized in that the grinding is performed by ball milling.
8. The method for preparing modified nano titanium dioxide material according to claim 7, wherein the grinding medium used for ball milling is zirconia beads.
9. The method for preparing modified nano titanium dioxide material according to claim 8, wherein the zirconia beads have a particle size of 0.1mm to 0.5 mm.
10. The method for preparing modified nano titanium dioxide material according to claim 7, wherein the ball milling conditions comprise: the rotating speed is 200 r/min-800 r/min; the time is 1-8 h.
11. The preparation method of the modified nanometer titanium dioxide material as claimed in claim 6, wherein the mass ratio of the nanometer titanium dioxide to the dispersion medium is 1: 100-1: 10000.
12. The method for preparing the modified nano titanium dioxide material according to any one of claims 6 to 11, wherein the dispersion medium is water.
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